CN1128178A - 烯烃水合方法 - Google Patents
烯烃水合方法 Download PDFInfo
- Publication number
- CN1128178A CN1128178A CN95119689A CN95119689A CN1128178A CN 1128178 A CN1128178 A CN 1128178A CN 95119689 A CN95119689 A CN 95119689A CN 95119689 A CN95119689 A CN 95119689A CN 1128178 A CN1128178 A CN 1128178A
- Authority
- CN
- China
- Prior art keywords
- acid
- ion
- composition
- niobium oxide
- hydration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000006703 hydration reaction Methods 0.000 title claims description 33
- 230000036571 hydration Effects 0.000 title claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 10
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 27
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 125000004429 atom Chemical group 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- -1 rhodium ion Chemical class 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 235000013495 cobalt Nutrition 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- HROWWQICXRYABV-UHFFFAOYSA-N P(=O)(O)OP(=O)O.[Mo] Chemical compound P(=O)(O)OP(=O)O.[Mo] HROWWQICXRYABV-UHFFFAOYSA-N 0.000 claims description 2
- 241000908838 Parietaria mottle virus Species 0.000 claims description 2
- 241001168730 Simo Species 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001439 antimony ion Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006187 pill Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- AMAGVGJJHVRPSI-UHFFFAOYSA-N potassium vanadium Chemical compound [K].[V] AMAGVGJJHVRPSI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 230000000887 hydrating effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- MAKKVCWGJXNRMD-UHFFFAOYSA-N niobium(5+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] MAKKVCWGJXNRMD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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Abstract
本发明涉及在催化剂体系存在下烯烃水合成相应醇的汽相方法。该催化剂体系包含载于氧化铌之上的杂多酸。使用氧化铌作载体不仅可以增加方法的时空产率，而且可以延长载体的使用寿命，因而减少载体更换的频次。此方法尤其适用于从乙烯生产乙醇和从丙烯生产异丙醇。
Description
本发明涉及新的催化剂组合物，它包括载于氧化铌上的杂多酸，及其作为催化剂在烯烃水合转化为醇的方法中的应用。
众所周知，使用沉积在硅质载体上的磷酸催化剂使烯烃如乙烯或丙烯水合转化为相应醇的汽相方法。许多现有技术发表物描述了这样的方法。这些发表物包括：GB-A-1570650，US-A-4808559，GB-A-1371905，US-A-4038211，US-A-4012452，GB-A-1476534，GB-A-1306141，US-A-3996338和CAN-A-844004。在每篇以上发表物中，所使用的硅质载体的性能是用许多参数限定的：包括孔体积，表面积、粉碎强度和载体纯度。但是没有一篇文献公开过为实现本发明目的的载体与杂多酸催化剂的精确组合。
一些现有技术发表物如GB-A-1281120描述了使用杂多酸催化剂使烯烃水合的液相方法。另外，US-A-2173187描述了使用杂多酸催化剂使烯烃水合成相应醇的汽相方法，该杂多酸的配位阴离子包括周期表中第VI族，A亚族的一种元素。此文献写到催化剂可以在有或没有载体下使用。当使用载体时载体优选为硅胶，虽然也列出其它硅质载体如硅酸、日本酸性粘土、膨润土、硅藻土或石棉。类似地，JA-A-57130935也描述了使用载在活性炭上的杂多酸进行烯烃水合的方法。还有，US-A-2608534描述了载于主要量的无机金属氧化物或氢氧化物上的杂多酸作为许多一般有机反应(尤其包括烯烃水合的反应)的催化剂。在此发表物中公开的载体有氧化铝、氧化镁、氧化钍、氧化钛等和优选为氧化铝。但是，并未公开用于烯烃水合成相应醇催化剂和具体方法。
现已发现载于氧化铌上的杂多酸是一种新型催化剂，它可以改善杂多酸催化体系的功能。
据此，本发明是包含载于氧化铌上的杂多酸的催化剂组合物。
适宜的氧化铌载体具有平均表面积至少为100米2/克，较好为大于150米2/克。另外，氧化铌必须具有平均破碎强度至少为2公斤力，较好至少为5公斤力，更好至少为6公斤力和最好至少为7公斤力。所说的粉碎强度是基于在一台CHATTILLON测试仪上对每批50个珠/球进行测定的平均值。该仪器测量在平行板之间破碎一个粒子所需的最小力。载体的松密度适宜为至少380克/升，较好为至少440克/升。氧化铌载体具有平均粒径2-10毫米，较好为4-6毫米。氧化铌载体适宜具有平均孔体积为0.1-1.2毫升/克，较好为0.3-1.0毫升/克。氧化铌载体适宜地具有平均孔径(使用前)为10-1000埃，较好为30-500埃。
此类载体的例子包含氧化铌水合物(Nb2O5·nH2O，由CBMM，Araxa，Brazil供货)。所用的氧化铌载体可以是任何形状或形式，但在用杂多酸浸渍前适且地为丸粒、挤出物、颗粒、珠粒的形式或为球形。
为了获得最佳功能，氧化铌载体适宜地不含有可能对体系的催化活性带来不良影响的外加金属或元素。氧化铌载体适宜地具有至少80％(重/重)的纯度(相对于氧化铌的含量来说)，即对体系的催化活性可能带来不良影响的杂质要低于20％(重/重)，较好为低于10％(重/重)和更好为低于5％(重/重)。
本说明书所用的术语“杂多酸”是指包括它们的游离酸及其盐。用于制备本发明烯烃水合催化剂的杂多酸因此包括它们的游离酸及其配位型盐，其中阴离子是高分子量的配位体。典型地，此阴离子含有2-18氧链的多价金属原子，它们称之为外围原子。这些外围原子以对称方式围绕一个或几上中心原子。外围原子通常是一个或多个的钼、钨、钒、铌、钽和其它金属。中心原子通常是硅或磷，但可包括周期表中第I-VIII族的许多元素中的任何一个。这包括例如锂离子；铜离子；二价的铍、锌、钴或镍离子；三价的硼、铝、镓、铁、铈、砷、锑、磷、铋、铬、或铑离子；四价的硅、锗、锡、钛、锆、钒、硫、碲、锰、镍、铂、钍、铪、铈离子和其它希土离子；五价的磷、砷、钒、锑离子；六价的碲离子；和七价的碘离子。这类杂多酸也称之为“多氧阴离子”，“多氧金属酸盐”或“金属氧化物簇”。有些熟知的阴离子的结构是以此领域原研究者的名字命名的，例如称之为Keggin，Wells-Dawson和Anderson-Evans-Perloff结构。
杂多酸通常有高分子量，如在700-8500范围内，且包括双重配合物(dimenc complexes)。它们在极性溶剂中有相当高的溶解度，这些溶剂如水或其它含氧溶剂，尤其是当杂多酸是游离酸和在某些盐的情况下。另外选择适宜的反离子可以控制它们的溶解度。在本发明中用作催化剂的杂多酸的具体例子包括。
1-12-钨磷酸-H3[PW12O40].xH2O
1-12-钼磷酸-H3[PMo12O40].xH2O
1-12-钨硅酸-H4[SiW12O40].xH2O
1-12-钼硅酸-H4[SiMo12O40].xH2O
钨磷酸钾- K6[P2W18O62].xH2O
钼磷酸钠- Na3[PMo12O40].xH2O
钼二磷酸铵- (NH4)6[P2Mo18O62].xH2O
钨镍酸钠- Na4NiW6O24H6].xH2O
钼二钴酸铵- (NH4)[Co2Mo10O36].xH2O
钨硅酸氢铯- Cs3H[SiW12O40].xH2O
钼二钒磷酸钾-K5[PMoV2O40].xH2O
钨硅酸氢铜- CuH2[SiW12O40].xH2O
钨硅酸氢锂- Li3H[SiW12O40].xH2O
氧化铌载体适宜地用杂多酸溶液浸渍，而这种杂多酸溶液是将杂多酸溶解在如乙醇或蒸馏水中来制备的。载体加到所制备的溶液中。在此溶液中载体适宜地浸泡几小时，不时手动搅拌然后用布氏漏斗过滤，以除去过量的酸。其它浸渍技术如初湿技术(incipent wetnesstechnique)也可以使用。
这样生成的湿催化剂适宜地放入烘箱中升温干燥几小时，然后在保干器中冷却至室温。干燥催化剂的重量减去所用氧化铌载体的重量就可得到杂多酸在载体上的负载量(克/升)。此催化剂(称重后)用于烯烃水合方法中。
应当指出，前述和用一些具体化合物的典型化学式表示的杂多酸的多价氧化态仅适用于在浸渍于氧化铌载体之前和尤其是在施加烯烃水合条件之前的新鲜的酸。杂多酸的水合度影响催化剂的酸度，因而也影响它的活性。因此，浸渍和/或烯烃水合条件这些作用均可能改变杂多酸内金属的氧化态和水合度，即在方法条件下实际催化的物质可能并不保持在浸渍载体时使用的杂多酸中金属的水合度/氧化态。因此，可以预期，反应后的用过的催化剂，其水合度和氧化态也可能是不同的。
可以加入磷酸或其它无机酸来使载体杂多酸催化剂进一步改性。
根据本发明的进一步实施，本发明也涉及在含有载于氧化铌上的杂多酸的催化剂体系存在下使烯烃水合成相应醇的汽相方法。
此方法适宜在下述反应条件下进行：
a.通过反应器的水对烯烃的摩尔比适宜地为0.1-3.0，较好为0.1-1.0；
b.水/烯烃混合物的气体时空速度(GHSV)适宜为0.010-0.25克/分/厘米3催化剂体系，较好为0.03-0.10克/分/厘米3；
c.以催化剂总重为基，杂多酸催化剂的浓度为5-40％(重/重)，较好为10-30％(重/重)。
烯烃水合反应是在温度150-350℃范围内进行。在此范围内，乙烯水合成乙醇是在其露点至350℃，较好为200-300℃，的温度下进行；丙烯水合成异丙醇是在其露点至300℃，较好为150-250℃，的温度下进行。
适宜的进行水合的烯烃是乙烯或丙烯，和这样得到的相应的醇分别是乙醇和异丙醇，这些烯烃可以是纯的或是烯烃混合物，后者则得到相应的醇的混合物。来自炼厂(如流态化催化裂解工艺)和包括C2和C3饱和和不饱和烃的混合烃进料可以用于本发明。此方法在汽相下进行，即烯烃和水是以汽相通过催化剂体系，而不管每种气体反应物的小部分会溶解在催化剂体系中。但据认为水合反应是发生在这种溶解的反应物之间的。在反应期间相应于烯烃的醚也以副产物而生成。
水合反应是这样进行的：将催化剂体系放进反应器中，密封反应器和然后加热催化剂体系至反应温度。视所需的最终产物而定，催化剂体系加热至170-300℃的温度。例如，如最终产物是从乙烯得到的乙醇，催化剂体系适宜地加热至225-280℃，较好为230-260℃，更好为235-245℃。而另一方面，如最终产物是从丙烯得到的异丙醇，则催化剂体系适宜地加热至180-225℃，较好为185-205℃。当催化剂体系达到所需温度，汽相的烯烃和水进料通过反应器。通过反应器的水对烯烃的摩尔比适宜为0.1-3.0，较好为0.1-1.0。更好为0.25-0.45。水蒸汽/烯烃混合物通过反应器的空速要看烯烃反应剂是乙烯还是丙烯而略加调整。例如是乙烯时它与水蒸汽的混合物的空速适宜为0.01-0.100，较好为0.020-0.050克/分/厘米3催化剂体系。如是丙烯和水蒸汽的混合物时，空速适宜为0.010-0.100，较好为0.02-0.07克/分/厘米3催化剂体系。
水合反应是在压力1000-25000KPa范围内进行。在此范围内，乙烯的水合适宜在3000-10000KPa下进行；而丙烯的水合适宜在2000-7600KPa下进行。
催化剂体系的活性这样测量，测定在标准测试条件下(具体见下述实例)在一小时内产生的醇、醚和未反应烯烃的总量。
用气相色谱测量醇和醚的产量(见后)，而未反应的烯烃则用湿式正取代流量计来计量。
因此，现已发现，由于使用了本文所描述的具体的氧化铌载体，不仅可以增加方法的时空产率(此后称“STY”)，而且可以延长载体的寿命，以减少载体在设备中更换的频率。
本发明参考下述实例进一步说明本发明。
实例1
所使用的一般程序和设备的描述
载体的催化剂(20毫升)装入微型反应器。充入惰性气体氮气(413毫升/分)使压力增至6800KPa，和温度升至260℃(以每分种升1℃的速度)。实例中所用的催化剂的质量表示于后。当温度稳定在260℃时，通入水(以0.11毫升液体/分的速度)，同时保持惰性的氮气流。水/氮气流持续30分钟。停止氮气流，和以约1240/小时的气体时空速度(GHSV)通入乙烯。水/乙烯摩尔比为0.3。测量催化剂活性(见下列表1的结果)。收集2-3小时的产物和用GC分析气体和液体进料。在260℃和240℃评价催化剂。
在本例中乙烯的水合是使用载于氧化铌上的硅钨酸催化剂。载体催化剂是这样制备的：将硅钨酸[H4SiW12O40](18.18克)溶于蒸馏水中(50％毫升)。此溶液与粉碎的氧化铌(33.74克)混合。该粉碎的氧化铌是将CBMM，Araxa，Brazil供给的细粒氧化铌水合物(Nb2O5·nH2O)在10吨力作用下制片，然后将所得的片粉碎至1.0-1.4毫米的粒度。这氧化铌载体和酸溶液的混合物不时搅拌下放置24小时。过滤除去载体催化剂的过量的酸。经过滤的载体催化剂在120℃干燥过夜。干燥后载体催化剂的质量为34.88克。
此实例的目的是在标准条件下(乙烯的GHSV为1240/小时，水/乙烯摩尔比为0.3，温度260℃和压力6800KPa)试验和然后观测降低施用温度的效果。水流相对于乙烯的摩尔比定在0.33。所用载体催化剂的体积是20厘米3和所用载体催化剂的质量是24.6克。所用的载体催化剂的丸粒大小为1.0-1.4毫米。计算了在标准温度和压力下的GHSV。所用的反应条件和得到的结果见下表1。
表1
*-选择性
| HOS | 温度(℃) | 压力(KPa) | H2O∶C2H4摩尔比 | GHSVC2H4 | 克/升催化剂/小时 | 转化率％摩尔 | Sely*C2％摩尔 | STY克/升催化剂/小时 | ||||
| C2H4 | H2O | C2H4 | H2O | 乙醇 | 乙醚 | 乙醇 | 乙醚 | |||||
| 4 | 260 | 6800 | 0.38 | 1095 | 1368 | 330 | 2.0 | 4.9 | 83 | 17 | 38 | 6 |
| 6 | 260 | 6800 | 0.33 | 1228 | 1535 | 330 | 3.1 | 8.2 | 76 | 24 | 60 | 15 |
| 10 | 260 | 6800 | 0.36 | 1141 | 1426 | 330 | 2.5 | 6.6 | 89 | 11 | 52 | 5 |
| 12 | 260 | 6800 | 0.35 | 1181 | 1476 | 330 | 2.7 | 7.4 | 90 | 10 | 59 | 6 |
| 14 | 260 | 6800 | 0.34 | 1210 | 1513 | 330 | 2.5 | 7.0 | 90 | 10 | 56 | 5 |
| 18 | 240 | 6800 | 0.35 | 1182 | 1478 | 330 | 1.0 | 2.9 | 100 | 0 | 24 | 0 |
| 20 | 240 | 6800 | 0.33 | 1245 | 1556 | 330 | 0.9 | 2.6 | 95 | 5 | 22 | 1 |
| 22 | 240 | 6800 | 0.33 | 1236 | 1545 | 330 | 0.9 | 2.6 | 98 | 2 | 22 | 0 |
Claims (21)
1.一种催化剂组合物，此组合物包含载于氧化铌上的杂多酸。
2.权利要求1的组合物，其中氧化铌载体的表面积大于100米2/克。
3.权利要求1的组合物，其中氧化铌载体通过造粒或挤压成型为丸粒或珠粒或球形。
4.权利要求1的组合物，其中氧化铌载体的平均粒径为2-10毫米，平均孔体积为0.3-1.2毫升/克，平均孔径(使用前)为10-1000埃，松密度为至少380克/升和平均粉碎强度至少为2公斤力。
5.权利要求1的组合物，其中氧化铌载体不含有外加金属或元素和相对于铝硅酸盐含量来说至少具有80％(重/重)的纯度。
6.权利要求1的组合物，其中所用的杂多酸催化剂选自游离杂多酸或其配位盐，包括与阴离子配位的中心原子，其中阴离子是高分子量的配位体和包括2-18个氧链的多价金属的外围原子，这些外围原子围绕选自元素周期表第I-VIII族的中心原子或离子。
7.权利要求6的组合物，其中多价金属的外围原子是一个或多个的钼、钨、钒、铌和钽，和中心原子或离子是选自锂离子；铜离子；二价的铍、锌、钴或镍离子；三价的硼、铝、镓、铁、铈、砷、锑、磷、铋、铬、或铑离子；四价的硅、锗、锡、钛、锆、钒、硫、碲、锰、镍、铂、钍、铪、铈离子和其它希土离子；五价的磷、砷、钒、锑离子；六价的碲离子；和七价的碘离子。
8.权利要求1的组合物，其中杂多酸催化剂选自：
1-12-钨磷酸-H3[PW12O40].xH2O
1-12-钼磷酸-H3[PMo12O40].xH2O
1-12-钨硅酸-H4[SiW12O40].xH2O
1-12-钼硅酸-H4[SiMo12O40].xH2O
钨磷酸钾- K6[P2W18O62].xH2O
钼磷酸钠- Na3[PMo12O40].xH2O
钼二磷酸铵- (NH4)6[P2Mo18O62].xH2O
钨镍酸钠- Na4[NiW6O24H6].xH2O
钼二钴酸铵- (NH4)[Co2Mo10O36].xH2O
钨硅酸氢铯- Cs3H[SiW12O40].xH2O
钼二钒磷酸钾-K5[PMoV2O40].xH2O
钨硅酸氢铜- CuH2[SiW12O40].xH2O
钨硅酸氢锂- Li3H[SiW12O40].xH2O。
9.烯烃水合成相应醇的汽相方法，该方法使用包含载于氧化铌上的杂多酸催化剂的催化剂体系。
10.权利要求9的方法，其中所述的催化剂体系为前述权利要求1-8所限定的任一组合物。
11.权利要求9的方法，其中用于烯烃水合反应的载体杂多酸催化剂可加入磷酸或其它无机酸而再改性。
12.权利要求9的方法，其中水合反应在1000-25000KPa的压力下进行。
13.权利要求9的方法，其中待水合的烯烃是纯烯烃或得到相应醇混合物的烯烃混合物。
14.权利要求9的方法，其中烯烃反应物是来自炼厂的混合烃进料和包括C2和C3的饱和和不饱和的烃的混合物。
15.权利要求9的方法，其中烯烃水合反应是在150-350℃的温度下进行。
16.权利要求9的方法，其中乙烯水合成乙醇是在进料气的露点至350℃的温度下进行。
17.权利要求16的方法，其中所述水合反应是在200-300℃温度下进行。
18.权利要求16的方法，其中乙烯与水蒸汽的混合物的空速为0.020-0.050克/分/厘米3催化剂体系。
19.权利要求9的方法，其中丙烯水合成异丙醇是在进料气的露点至300℃的温度下进行的。
20.权利要求19的方法，其中所述水合反应是在150-250℃的温度下进行的。
21.权利要求19的方法，其中丙烯与水蒸汽的混合物的空速为0.020-0.070克/分/厘米2催化剂体系。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9423646.0 | 1994-11-23 | ||
| GB9423646A GB9423646D0 (en) | 1994-11-23 | 1994-11-23 | Olefin hydration process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1128178A true CN1128178A (zh) | 1996-08-07 |
Family
ID=10764862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95119689A Pending CN1128178A (zh) | 1994-11-23 | 1995-11-23 | 烯烃水合方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5616815A (zh) |
| EP (1) | EP0713723A1 (zh) |
| JP (1) | JPH08224480A (zh) |
| KR (1) | KR960016956A (zh) |
| CN (1) | CN1128178A (zh) |
| CA (1) | CA2163324A1 (zh) |
| GB (1) | GB9423646D0 (zh) |
| SG (1) | SG46963A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094481C (zh) * | 1999-12-30 | 2002-11-20 | 中国科学院广州能源研究所 | 从催化裂化干气中分离回收乙烯的方法及其装置 |
| CN102206135A (zh) * | 2011-03-23 | 2011-10-05 | 中国科学院山西煤炭化学研究所 | 一种3-甲基-1,3-丁二醇的制备方法 |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0836121B1 (en) * | 1996-10-09 | 2001-06-06 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, and image forming method |
| US6043184A (en) * | 1998-01-05 | 2000-03-28 | Sunoco, Inc. (R&M) | Heteropoly acids supported on polyoxometallate salts and their preparation |
| US6060419A (en) | 1998-01-05 | 2000-05-09 | Sunoco, Inc. (R&M) | Wells-Dawson type heteropolyacids, their preparation and use as oxidation catalysts |
| GB9806408D0 (en) * | 1998-03-25 | 1998-05-20 | Bp Chem Int Ltd | Olefin hydration process |
| GB9809210D0 (en) * | 1998-04-29 | 1998-07-01 | Bp Chem Int Ltd | Olefin hydration process |
| EP1077082A1 (en) * | 1999-08-17 | 2001-02-21 | Rohm And Haas Company | Heteropolyacid/polyoxometallate catalysts |
| US7514577B2 (en) * | 2006-05-31 | 2009-04-07 | Exxonmobil Chemical Patents Inc. | Pd- and Pt-substituted polyoxometalates and process for their preparation |
| US7820868B2 (en) * | 2007-01-19 | 2010-10-26 | Exxonmobil Chemical Patents Inc. | Transition metal substituted polyoxometalates and process for their preparation |
| US7645907B2 (en) * | 2007-03-23 | 2010-01-12 | Exxonmobil Chemical Patents Inc. | Transition metal substituted polyoxometalates and process for their preparation |
| US8558036B2 (en) | 2010-11-15 | 2013-10-15 | Saudi Arabian Oil Company | Dual phase catalysts system for mixed olefin hydrations |
| US8629080B2 (en) | 2011-03-21 | 2014-01-14 | Saudi Arabian Oil Company | Hydrated niobium oxide nanoparticle containing catalysts for olefin hydration |
| DE102017000861A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Synthese eines MoVTeNb-Katalysators aus preisgünstigen Metalloxiden |
| DE102017000848A1 (de) * | 2017-01-31 | 2018-08-02 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur Herstellung molybdänhaltiger Mischoxidmaterialien |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA844004A (en) | 1970-06-09 | C. Hull David | Manufacture of a catalyst for the vapor phase hydration of olefins | |
| FR815020A (fr) * | 1935-12-24 | 1937-07-05 | Carbide & Carbon Chem Corp | Procédé de fabrication d'alcools et d'éthers aliphatiques par hydratation catalytique d'oléfines |
| US2173187A (en) | 1937-02-25 | 1939-09-19 | Du Pont | Process for hydrating olefins |
| US2608534A (en) | 1949-04-18 | 1952-08-26 | Union Oil Co | Heteropoly acids or salts thereof as catalysts |
| GB1306141A (zh) | 1969-04-01 | 1973-02-07 | ||
| JPS4936203B1 (zh) | 1969-05-08 | 1974-09-28 | ||
| GB1371905A (en) | 1971-07-27 | 1974-10-30 | Bp Chem Int Ltd | Olefin hydration catalyst and use thereof in alcohol production |
| US3996338A (en) | 1973-12-17 | 1976-12-07 | National Distillers And Chemical Corporation | Silica xerogel |
| US4038211A (en) | 1973-12-17 | 1977-07-26 | National Distillers And Chemical Corporation | Olefin hydration catalyst |
| US4012452A (en) | 1973-12-17 | 1977-03-15 | National Distillers And Chemical Corporation | Olefin hydration process |
| SE7413470L (zh) | 1974-01-14 | 1975-07-15 | Nat Distillers Chem Corp | |
| DE2658946C2 (de) | 1976-12-24 | 1984-06-07 | Chemische Werke Hüls AG, 4370 Marl | Verfahren zur Herstellung von Alkoholen mit 2-3 C-Atomen |
| US4212990A (en) * | 1977-08-05 | 1980-07-15 | Toray Industries, Inc. | Method for producing cyclohexane derivatives directly from aromatic hydrocarbons |
| JPS57130935A (en) | 1981-02-09 | 1982-08-13 | Tokuyama Soda Co Ltd | Hydrating method of olefin |
| JPS6154241A (ja) * | 1984-08-21 | 1986-03-18 | シ−ビ−エムエム・インタ−ナシヨナル・リミタ−ダ | 含水酸化ニオブ固体酸触媒 |
| DE3709401A1 (de) | 1987-03-21 | 1988-09-29 | Huels Chemische Werke Ag | Verfahren zur herstellung eines katalysators fuer die hydratation von olefinen zu alkoholen |
| US4877764A (en) * | 1987-04-20 | 1989-10-31 | The Standard Oil Company | Catalyst system for ammoxidation of paraffins |
| US4769355A (en) * | 1987-04-20 | 1988-09-06 | The Standard Oil Company | Catalyst system for ammoxidation of paraffins |
| DE4102328A1 (de) * | 1991-01-26 | 1992-07-30 | Degussa | Pyrogen hergestelltes nioboxid |
-
1994
- 1994-11-23 GB GB9423646A patent/GB9423646D0/en active Pending
-
1995
- 1995-11-09 EP EP95308012A patent/EP0713723A1/en not_active Withdrawn
- 1995-11-13 US US08/556,646 patent/US5616815A/en not_active Expired - Fee Related
- 1995-11-20 CA CA002163324A patent/CA2163324A1/en not_active Abandoned
- 1995-11-22 SG SG1995001890A patent/SG46963A1/en unknown
- 1995-11-22 JP JP7328221A patent/JPH08224480A/ja active Pending
- 1995-11-23 CN CN95119689A patent/CN1128178A/zh active Pending
- 1995-11-23 KR KR1019950043251A patent/KR960016956A/ko not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094481C (zh) * | 1999-12-30 | 2002-11-20 | 中国科学院广州能源研究所 | 从催化裂化干气中分离回收乙烯的方法及其装置 |
| CN102206135A (zh) * | 2011-03-23 | 2011-10-05 | 中国科学院山西煤炭化学研究所 | 一种3-甲基-1,3-丁二醇的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0713723A1 (en) | 1996-05-29 |
| SG46963A1 (en) | 1998-03-20 |
| GB9423646D0 (en) | 1995-01-11 |
| KR960016956A (ko) | 1996-06-17 |
| CA2163324A1 (en) | 1996-05-24 |
| US5616815A (en) | 1997-04-01 |
| JPH08224480A (ja) | 1996-09-03 |
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